Center Court at the Lindner Family Tennis Center in Cincinnati, Ohio, will be the site for this highly anticipated battle, scheduled to get underway at 7 p.m. EST (6 p.m. CST/) on ESPN-2 and ATP live stream.
The top-seeded American looks to continue her dominant ways as she goes for a seventh consecutive victory over her Chinese counterpart.
Last time Williams and Li met was at this year's Sony Open quarter-finals in March. With the home-crowd behind her, the 16-time Grand Slam champion cruised in straight-sets, ultimately capturing her sixth Miami Masters title.
However, it's hard to believe that Williams has yet to leave her imprint in the city of Cincinnati. As she chases her first ever Rookwood Cup, Serena admitted getting off to a slow start in the final tune-up before the 2013 US Open.
I definitely haven't felt good all week, so surprised I'm still in the event. It's not really about how you play at the end. It's about being able to win, whether you play good or bad. I was able to so far and be in the semi-finals. So, you know, considering, it's a good result. I obviously want to do better, and I'll just see how it goes.
If tennis oddsmakers prove to be correct, Williams shouldn't have a problem moving on to the finals by improving her head-to-head mark to 9-1 against Li Na.
Even if she hasn't been at her best, Las Vegas betting experts list Serena Williams as a mammoth 1/10 [-1000] favorite over her 11/2 [+550] underdog opponent.
The winner of this match will face either Victoria Azarenka or Jelena Jankovic in the 2013 Western and Southern Open women's singles finals tomorrow.